U.S. patent application number 13/141276 was filed with the patent office on 2011-10-20 for hydraulically setting sealing composition.
This patent application is currently assigned to Wacker Chemie AG. Invention is credited to Jurgen Bezler, Dimitrios Moussios, Mohammed Sanaobar.
Application Number | 20110257303 13/141276 |
Document ID | / |
Family ID | 44487019 |
Filed Date | 2011-10-20 |
United States Patent
Application |
20110257303 |
Kind Code |
A1 |
Moussios; Dimitrios ; et
al. |
October 20, 2011 |
Hydraulically Setting Sealing Composition
Abstract
The invention provides hydraulically setting sealing composition
based on a) a hydraulically setting compound out of the group
comprising high-alumina cement, ordinary portland cement, blast
furnace slag, b) protective-colloide stabilized polymer of one or
more ethylenically unsaturated monomers in form of an aqueous
polymer dispersion or a water-redispersible polymer powder, and c)
one or more fillers.
Inventors: |
Moussios; Dimitrios; (Dubai,
AE) ; Bezler; Jurgen; (Burghausen, DE) ;
Sanaobar; Mohammed; (Dubai, AE) |
Assignee: |
Wacker Chemie AG
Munich
DE
|
Family ID: |
44487019 |
Appl. No.: |
13/141276 |
Filed: |
December 17, 2009 |
PCT Filed: |
December 17, 2009 |
PCT NO: |
PCT/EP2009/067359 |
371 Date: |
June 21, 2011 |
Current U.S.
Class: |
524/5 ; 524/2;
524/7; 524/8 |
Current CPC
Class: |
Y02W 30/94 20150501;
Y02W 30/91 20150501; C04B 2103/0065 20130101; C04B 2103/0057
20130101; C04B 28/08 20130101; C04B 2111/00508 20130101; C04B
2111/26 20130101; C04B 2111/24 20130101; C04B 28/04 20130101; C04B
28/06 20130101; C04B 2111/00482 20130101; C04B 28/04 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/06 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/08 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/04 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/06 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/08 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/04 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/06 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/08 20130101; C04B
24/26 20130101; C04B 2103/0054 20130101; C04B 28/04 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/06 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/08 20130101; C04B
24/26 20130101; C04B 2103/0057 20130101; C04B 28/04 20130101; C04B
14/06 20130101; C04B 14/28 20130101; C04B 16/0658 20130101; C04B
18/146 20130101; C04B 24/06 20130101; C04B 24/2623 20130101; C04B
24/383 20130101; C04B 28/06 20130101; C04B 7/32 20130101; C04B
14/06 20130101; C04B 14/28 20130101; C04B 16/0658 20130101; C04B
18/146 20130101; C04B 24/06 20130101; C04B 24/2676 20130101; C04B
24/383 20130101; C04B 28/08 20130101; C04B 14/06 20130101; C04B
14/28 20130101; C04B 16/0658 20130101; C04B 18/146 20130101; C04B
24/06 20130101; C04B 24/2641 20130101; C04B 24/383 20130101 |
Class at
Publication: |
524/5 ; 524/2;
524/7; 524/8 |
International
Class: |
C04B 24/26 20060101
C04B024/26; C09D 131/04 20060101 C09D131/04; C09D 125/10 20060101
C09D125/10; C09D 127/06 20060101 C09D127/06 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 22, 2008 |
AE |
1293/2008 |
Claims
1. Hydraulically setting sealing composition based on a) a
hydraulically setting compound out of the group comprising
high-alumina cement, ordinary portland cement, blast furnace slag,
b) protective-colloide stabilized polymer of one or more
ethylenically unsaturated monomers in form of an aqueous polymer
dispersion or a water-redispersible polymer powder, and c) one or
more fillers.
2. The cementitious sealing composition as claimed in claim 1
comprising a combination of high-alumina cement and blast furnace
slag.
3. The cementitious sealing composition as claimed in claim 1
comprising ordinary portland cement as the only component a).
4. The cementitious sealing composition as claimed in claim 1
comprising blast furnace slag as the only component a).
5. The cementitious sealing composition as claimed in claims 1 to
4, wherein polymers b) used are vinyl acetate homopolymers,
copolymers of vinyl acetate with ethylene, copolymers of vinyl
acetate with ethylene and with one or more other vinyl esters,
copolymers of vinyl acetate with ethylene and (meth)acrylic ester,
copolymers of vinyl acetate with (meth)acrylates and other vinyl
esters, copolymers of vinyl acetate with ethylene and vinyl
chloride, copolymers of vinyl acetate with acrylates,
styrene-acrylic ester copolymers, styrene-1,3-butadiene copolymers,
vinyl chloride-ethylene-copolymers.
6. The use of the cementitious sealing composition as claimed in
any of claims 1 to 5 as a coating for the protection of concrete
materials.
7. The use of the cementitious sealing composition as claimed in
claim 6 as a salt resistant coating for concrete structures which
are exposed to seawater.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is the national phase filing of
international patent application No. PCT/EP2009/067359, filed 17
Dec. 2009, and claims priority of United Arab Emirates patent
application number 1293/2008, filed 22 Dec. 2008, the entireties of
which applications are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention concerns hydraulically setting sealing
compositions for the protection of concrete structures.
BACKGROUND OF THE INVENTION
[0003] Accelerated deterioration of reinforced concrete structures
is a well reported phenomenon. It occurs particularly in regions
with aggressive environment. An example for such regions are the
coastal areas of the Arabian Gulf. The environmental conditions of
the Arabian Gulf are characterized by high temperature and
humidity. Due to the closed nature of the Arabian Gulf, the
salinity of the seawater is more than that in other areas of the
world. The same is right for the salt concentration in the air,
particularly in coastal regions. Such climatic effects reduces
significantly the durability of concrete structures as well on
shore as offshore.
[0004] Coppola L. et al, American Concrete Institute, SP (2000),
SP-192-73, p. 1209-1220 describe the use of sealing slurries for
the protection of concrete structures. The sealing slurries are
composed of an acrylic polymer emulsion, cement and metakaolin. In
JP 09-087061 a composition for coating concrete structures is
recommended, composed of a vinyl acetate ethylene copolymer
emulsion, which is stabilized with nonionic emulsifier, alumina
cement and silica sand. JP 03-039387 refers to a protection
material for concrete composed of a polymer latex, alumina cement,
transition metal oxide, iron oxide and sand. For the protection of
corrosion on a surface contacted with seawater JP 55-121869
recommends a double-layered coating, with a first layer built with
a mixture composed of aqueous polymer emulsion, portland cement or
blast furnace cement, and a topcoat composed of copper sulphate and
an aqueous polymer emulsion.
[0005] DE 3048818 A1 describes the improvement of concrete
structures with polymer latex compositions containing waxy
additives. Concrete modified with these latex compositions shows an
improved corrosion resistance in contact with salt water. The
coating of concrete structures with a curable polymer resin is the
subject of DE 3445396 A1. WO 86/04889 A1 concerns the utilization
of compositions based on polymer latex, aluminous cement and gypsum
for obtaining crack-free concrete compositions with low
water-permeability. U.S. Pat. No. 4,668,541 B describes a method
for protecting concrete structures against damages caused by
chloride-initiated corrosion. The method is characterized in that a
layer of slag-cement concrete is applied to the concrete structure.
The U.S. Pat. No. 4,894,405 is related to a coating composition
formed by a polyurethane component and an organosiloxane component.
The main objective is to stop corrosion generated by chlorine
ions.
SUMMARY OF THE INVENTION
[0006] It is an object of the invention to protect concrete
structures even if exposed in harmful environment, like marine or
splash zone environment where the conditions are severely
corrosive. The surface of the concrete structures shall be
protected against mechanical erosion due to wind (sand storms) or
pounding waves, too.
[0007] This object has surprisingly been able to be achieved by the
inventive combination of hydraulically setting components with a
polymer component.
DETAILED DESCRIPTION OF THE INVENTION
[0008] The invention provides hydraulically setting sealing
composition based on [0009] a) a hydraulically setting compound out
of the group comprising high-alumina cement, ordinary portland
cement, blast furnace slag, [0010] b) protective-colloid stabilized
polymer of one or more ethylenically unsaturated monomers in form
of an aqueous polymer dispersion or a water-redispersible polymer
powder, and [0011] c) one or more fillers.
[0012] In general the composition contains from 5% by weight to 50%
by weight of component a), preferably 5% by weight to 25% by
weight, in each case based on the total weight of the dry materials
a) to c).
[0013] Component a) comprises high-alumina cement or ordinary
portland cement or blast furnace slag. Preferred high-alumina
cement is calcium aluminate cement (CAC) according to DIN EN 14647.
Preferred ordinary portland cement is ordinary portland cement
(OPC) according to DIN EN 197-1 (CEM I to CEM V). In general blast
furnace slag contains 30 to 45% by weight CaO, 30 to 45% by weight
SiO.sub.2, 5 to 15% by weight Al.sub.2O.sub.3, 4 to 17% by weight
MgO, 0.5 to 1% by weight S and traces of further elements.
Commercially available blast furnace slag is Slagstar.RTM. of
Baumit or Merit 5000 of SSAB Merox.
[0014] In a preferred embodiment the components a) are used
alternatively in the composition. Particularly preferred as the
only component a) is blast furnace slag. Preferred combinations of
components a) are the combination of high-alumina cement with blast
furnace slag, or the combination of ordinary portland cement with
blast furnace slag. If combinations are used in the composition,
the composition contains from 5% by weight to 50% by weight of the
combination, preferably 5% by weight to 25% by weight, in each case
based on the total weight of the dry materials a) to c).
[0015] In general the composition contains from 10% by weight to
50% by weight, preferably from 10% by weight to 30% by weight of
the polymer b), in each case based on the total weight of the
components a) to c). In the case of polymer dispersions the amount
in % by weight refers to the solids content of the polymer
dispersions.
[0016] Preferably the aqueous polymer dispersion or the
water-redispersible polymer powder is based on polymers of one or
more monomers from the group consisting of vinyl esters,
(meth)acrylates, vinyl aromatics, olefins, 1,3-dienes and vinyl
halides and, if required, further monomers copolymerizable
therewith.
[0017] Examples of suitable homo- and copolymers are vinyl acetate
homopolymers, copolymers of vinyl acetate with ethylene, copolymers
of vinyl acetate with ethylene and with one or more other vinyl
esters, copolymers of vinyl acetate with ethylene and (meth)acrylic
ester, copolymers of vinyl acetate with (meth)acrylates and other
vinyl esters, copolymers of vinyl acetate with ethylene and vinyl
chloride, copolymers of vinyl acetate with acrylates,
styrene-acrylic ester copolymers, styrene-1,3-butadiene copolymers,
vinyl chloride-ethylene-copolymers.
[0018] Preference is given to vinyl acetate homopolymers;
Copolymers of vinyl acetate with from 1 to 40% by weight of
ethylene; Copolymers of vinyl acetate with from 1 to 40% by weight
of ethylene and from 1 to 50% by weight of one or more other
comonomers from the group of vinyl esters having from 1 to 15
carbon atoms in the carboxylic acid radical, e.g. vinyl propionate,
vinyl laurate, vinyl esters of alpha-branched carboxylic acids
having from 9 to 13 carbon atoms (versatic acids), such as VeoVa9,
VeoVa10, VeoVa11; Copolymers of vinyl acetate, from 1 to 40% by
weight of ethylene, and preferably from 1 to 60% by weight of
(meth)acrylic ester of unbranched or branched alcohols having from
1 to 15 carbon atoms, in particular N-butyl acrylate or
2-ethylhexyl acrylate; and Copolymers using from 30 to 75% by
weight of vinyl acetate, from 1 to 30% by weight of vinyl laurate
or vinyl esters of an alpha-branched carboxylic acid having from 9
to 13 carbon atoms, and also from 1 to 30% by weight of
(meth)acrylic esters of unbranched or branched alcohols having from
1 to 15 carbon atoms, in particular n-butyl acrylate or 2-ethyl
hexyl acrylate, where these also contain from 1 to 40% by weight of
ethylene; Copolymers using vinyl acetate, from 1 to 40% by weight
of ethylene, and from 1 to 60% by weight of vinyl chloride; where
the % by weight data in each case give a total of 100% by
weight.
[0019] Preference is also given to (meth)acrylate copolymers, for
example copolymers of n-butyl acrylate or 2-ethylhexyl acrylate, or
copolymers of methyl methacrylate with n-butyl acrylate and/or
2-ethylhexyl acrylate;
Styrene-acrylic ester copolymers using one or more monomers from
the group of methyl acrylate, ethyl acrylate, propyl acrylate,
n-butyl acrylate, 2-ethylhexyl acrylate; Vinyl acetate-acrylic
ester copolymers using one or more monomers from the group of
methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,
2-ethylhexyl acrylate, and, where appropriate, ethylene;
Styrene-1,3-butadiene copolymers; Vinyl chloride-ethylene
copolymers; where the % by weight data in each case give a total of
100% by weight.
[0020] Aqueous polymer dispersions and the water-redispersible
powders of the abovementioned polymers that are obtainable from
them by drying are known and are available commercially. The
polymers are prepared in a conventional manner, preferably by the
emulsion polymerization process. Processes for the preparation of
aqueous polymer dispersions and redispersible polymer powders are
described in WO 2004/092094, which is incorporated here by
reference.
[0021] The dispersions are stabilized with a protective colloid.
Suitable protective colloids are partially hydrolyzed or fully
hydrolyzed polyvinyl alcohols; polyvinylpyrrolidones;
polyvinylacetals; polysaccharides in water-soluble form such as
starches (amylose and amylopectin), celluloses and their
carboxymethyl, methyl, hydroxyethyl, and hydroxypropyl derivatives;
proteins such as casein or caseinate, soya protein, and gelatin;
lignin sulfonates; synthetic polymers such as poly(meth)acrylic
acid, copolymers of (meth)acrylates with carboxy-functional
comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids, and
the water-soluble copolymers thereof; melamine-formaldehyde
sulfonates, naphthalene-formaldehyde sulfonates, and styrene-maleic
acid and vinyl ether-maleic acid copolymers. Partially hydrolyzed
or fully hydrolyzed polyvinyl alcohols are preferred. Particular
preference is given to partially hydrolyzed polyvinyl alcohols
having a degree of hydrolysis of from 80 to 95 mol % and a Hoppler
viscosity in 4% strength aqueous solution of from 1 to 30 mPas
(Hoppler method at 20.degree. C., DIN 53015). Most preferred are
polymer compositions without emulsifier.
[0022] Suitable fillers c) are quartz sand, quartz flour, calcium
carbonate, dolomite, aluminum silicates, fumed silica, talc or
mica, fibers, or lightweight fillers such as pumice, foamed glass,
aerated concrete, perlites or vermiculites. Mixtures of said
fillers may also be used. The filler fraction is preferably from 10
to 90% by weight, with particular preference from 75 to 90% by
weight, in each case based on the total weight of the components a)
to c).
[0023] The sealing compositions may contain further common
ingredients out of the group of pozzolanic compounds, thickener,
retardants.
[0024] Most preferred further ingredients are additives having
pozzolanic properties (pozzolanas). Pozzolanas are
silica-containing or silica- and alumina-containing natural or
synthetic materials which are not themselves able to act as binders
but together with water and lime form water-insoluble compounds
having cement-like properties. A distinction is made between
natural and synthetic pozzolanas. Natural pozzolanas include
glass-rich ashes and rocks of volcanic origin, for example pumice,
trass (finely milled tuff), Santorin earth, kieselguhr, hornstones
(silica rocks), chert and moler earth. Synthetic pozzolanas include
fired, ground clay (ground brick), fly ashes such as ash from a
coal-fired power station, silica dust, oil shale ash (oil
shale=bituminous, lime-containing shale) and calcined kaolin
(metakaolin).
[0025] The synthetic pozzolanas are preferably selected from the
group consisting of ground brick, fly ash, silica dust, oil shale
ash and metakaolin. The greatest preference is given to fly ash or
silica dust. The amount used is from 0 to 20% by weight, preferably
from 0.5 to 10% by weight, in each case based on the total weight
of the dry materials a) to c).
[0026] Examples of thickeners are polysaccharides such as cellulose
ethers and modified cellulose ethers, starch ethers, guar gum or
xanthan gum, phyllosilicates, polycarboxylic acids such as
polyacrylic acid and the partial esters thereof, polyvinyl
alcohols, which optionally have been acetalized and/or
hydrophobically modified, casein, and associative thickeners. It is
also possible to use mixtures of these or other thickeners.
Preference is given to the cellulose ethers, modified cellulose
ethers, optionally acetalized and/or hydrophobically modified,
polyvinyl alcohols, and mixtures thereof. It is preferred to use
from 0.05 to 2.5% by weight, with particular preference from 0.05
to 0.5% by weight, of thickeners, in each case based on the total
weight of the dry materials a) to c).
[0027] Frequently used retardants have been selected from
hydroxycarboxylic acids or dicarboxylic acids or salts thereof, as
well as saccharides. Examples include oxalic acid, succinic acid,
tartaric acid, gluconic acid, citric acid, sucrose, glucose,
fructose, sorbitol and pentaerythritol. Further examples of
retarders are polyphosphates, metaphosphoric acid, and borax.
[0028] If the polymer component b) is used in form of a
redispersible polymer powder, the cementitious sealing compositions
is generally prepared by mixing components a) to c), and optionally
one or more of the above mentioned further ingredients, to a dry
mortar in conventional powder mixers and homogenizing the mixture.
The amount of water needed for processing is added immediately
prior to processing. Another possible procedure is to add
individual components only subsequently to the mixture prepared by
stirring with water.
[0029] If the polymer component b) is used in form of an aqueous
polymer dispersion, the components a) to c), and optionally further
ingredients, and if necessary an additional amount of water are
mixed for obtaining a pasty mortar.
[0030] The water ratio to be added to the dry mix depends on the
type of application. Usually water is added in an amount of 25% by
weight to 50% by weight, based on the dry weight of the
cementitious sealing composition.
[0031] The cementitious sealing composition is used as a coating
for the protection of concrete materials, particularly as a salt
resistant coating for concrete structures which are exposed to
seawater, especially at waterline (splash zone area).
EXAMPLES
[0032] For testing the cementitious sealing compositions the
following polymer components have been used:
Polymer 1:
[0033] Redispersible polymer powder on the basis of a vinyl
acetate-ethylene-copolymer with a glass transition temperature Tg
of -7.degree. C.
Polymer 2:
[0034] Redispersible polymer powder on the basis of a vinyl
acetate-ethylene-versatic acid ester-copolymer with a glass
transition temperature Tg of -14.degree. C.
[0035] The sealing slurry compositions of table 1 have been
prepared with the following method:
[0036] The constituents of the formulation were mixed dry for 3
minutes in a mortar mixer. The water was then added, and mixing was
continued for a further 2 minutes. After a maturing time of 10
minutes, the mortar was mixed for 30 seconds and then spread by
means of a trowel in a Teflon template to give a 2 mm thick sealing
coat, after drying it was removed from the template and then stored
at the following conditions:
28 days standard conditions (SC) 14 days SC+14 days water immersion
(WI) 14 days SC+7 days WI+7 days SC 7 days SC+21 days sea salt
water (30.degree. C.) (SSW) 7 days SC+21 days SSW+2 days SC
[0037] After storage, tensile bars were stamped from the sealing
coats and the tensile strength (N/mm.sup.2) and elongation at break
(%) of these were determined in a tensile test in accordance with
DIN 53504 on an Instron tensile tester at an extension rate of 10
mm/min. Crack bridging (mm) was determined according EN 14891.
[0038] The mean values of the individual series of measurements are
given in Table 1.
TABLE-US-00001 TABLE 1 Slurry 1 Slurry 2 Slurry 3 Formulation
(p.b.w.) (p.b.w) (p.b.w.) Ca aluminate cement (Fondu, Bomix) 70.0
Portland Cement OPC 200 Blast Furnace Slag (Slagstar.sup.R) 130.0
200 Polymer 1 Polymer 2 300.0 300 300 Silica sand (0-212.mu.) 300.0
400 400 CaCO.sub.3 (25.mu.) 134.0 Microsphere filler (Fillite) 50.0
Polyacrylonitrile fiber (3 mm) 5.0 5.0 5.0 Fumed silica (HDK H 15)
5.0 Tartaric acid 1.0 Thickener (Viscalex HV 100) 5.0 Total parts
by weight 1000.0 905.0 905.0 Water demand 320.0 310.0 310.0 Test
Result Hydrostatic Pressure (1.5 bars) Pass Pass Pass Tensile
strength (N/mm.sup.2) 28 days SC 2.30 2.50 2.00 14 days SC + 14
days WI 0.76 0.84 1.05 14 days SC + 7 days WI + 7 days SC 1.07 1.38
1.45 7 days SC + 21 days SSW 1.01 1.45 1.24 Elongation at break (%)
28 days SC 7.79 25.74 19.89 14 days SC + 14 days WI 5.34 7.88 11.03
14 days SC + 7 days WI + 7 days SC 3.31 8.78 15.04 7 days SC + 21
days SSW 8.47 17.17 10.66 Crack bridging (mm) 28 days SC 0.99 1.09
0.85 7 days SC + 21 days SSW 0.84 0.99 0.75 7 days SC + 21 days SSW
+ 2 days SC 0.76 1.14 0.61
* * * * *